JP6714023B2 - Articles with zeolite particles bound by resin - Google Patents

Description

The present invention relates to an adsorbent article comprising particles of zeolite and clay, said particles being bound together by a polymer, in particular an organic resin such as a thermoplastic polymer. The adsorbent has a high zeolite content, can ensure rapid diffusion of the fluid, and the immobilization of the particles in the article reduces wear between particles and even avoids them. Therefore, it is possible to improve the stability of the adsorbent.

US 2006/0166819 discloses resin-bound sorbents used as devices for air conditioning and freeze-drying. The sorbent is added as a powder, for example a zeolite powder, which powder is dispersed in the resin before pouring or molding. The sorbent content is relatively low (25 wt% to 55 wt%) and the adsorption rate is very slow, which makes the material less suitable when high adsorption and desorption rates are required.

WO2014/055546 improves on the above disclosure by creating some pores inside the composite material for rapid distribution of the fluid to be dried and for increasing the contact area between the fluid and the material. doing. If necessary, the uptake of moisture inside the material occurs relatively slowly. Such materials are envisioned to have low density and small volume. Again, the sorbent content is low (from 5 wt% to 55 wt%) and the adsorption rate remains slow.

WO2013/103433 is manufactured from sorbent or catalyst beads which are adhered onto a substrate (thin sheet or foil) by means of an adhesive such that they are wound in a spiral or arranged on a flat surface. Described articles. The beads are the customary adsorbents or catalysts. The article is proposed as a catalyst or sorbent that is more effective in catalysis and adsorption because the pressure drop of the liquid or gas through the layer of catalyst or sorbent is suppressed compared to a fixed bed. Has been done. Such articles of sorbent adhered to the substrate are rather difficult to manufacture due to the multiple components (sorbent, substrate and organic adhesive), which reduce the resistance of such articles. There is a risk that the sorbent will be stripped or desorbed from the substrate.

US 2008/0148936 discloses composite structure-type adsorbents containing a multi-channel framework made from ceramics, various inorganic oxides and adsorbent materials. Each channel contains adsorbent particles that are not immobilized within the article, so that the adsorbent particles are readily worn away.

US Patent Application Publication No. 2006/0166819 International Publication No. 2014/055546 International Publication No. 2013/103433 U.S. Patent Application Publication No. 2008/0148936

Thus, the adsorption and desorption rates are particularly intended for use where high adsorption rates are required, for example for dynamic separation of gases and/or liquids, such as pressure swing adsorption (PSA) and temperature swing adsorption (TSA). There is still a need for an adsorption treatment article (or adsorbent article) with high volumetric efficiency that is compatible with both.

The need for zeolite particles immobilized in the adsorbent layer to prevent any migration of the zeolite particles and thus avoid wear and dust formation while maintaining high separation efficiency (large volume and high reaction rate). Sex still exists.

Again, there is a need for an adsorbent article (or block) that has a high zeolite content, reduced attrition behavior of the particles together, limited pressure drop, and high diffusion rate.

The Applicant has now discovered that the adsorbent article of the present invention can meet all or at least some of the above needs and will now describe the adsorbent article of the present invention.

It is a sectional view of an example of an article (A) according to the present invention. 2 is a SEM image of a cross section of an article according to the invention illustrated by FIG. It is sectional drawing of an example of an adsorbent cartridge (B). It is sectional drawing of another example of the cartridge (C) which used the article (A). It is sectional drawing of an example of the cartridge (D) which used the article (A). FIG. 7 is an SEM image of a dried formulation obtained in step a) of the method described herein above, ie, prior to being immobilized by compression molding. FIG. 7 is an SEM image of another example of a dried formulation without inorganic resin obtained in step a) of the method described herein above, ie, prior to being immobilized by compression molding.

In a first embodiment, the present invention is an adsorbent article comprising zeolite particles of at least one zeolite adsorbent, said particles being immobilized by at least one resin, comprising at least one The average particle diameter of the zeolite adsorbent is 0.03 mm to 3 mm, preferably 0.04 mm to 2 mm, more preferably 0.05 mm to 1 mm, and the zeolite content is Is more than 60 wt%, more preferably more than 70 wt%, preferably more than exactly 80 wt%, more preferably more than exactly 85 wt%, even more preferably It preferably relates to an adsorbent article, generally more than 90 wt%, if strictly above 88 wt%.

In this specification, all numerical ranges include the upper and lower limits, unless stated otherwise. In the context of the present invention, "immobilized particles" means particles that exhibit reduced wear due to their inability to move within the article, and that exhibit significant mechanical integrity to become self-supporting.

According to a first preferred aspect of the present invention, the zeolite particles in the article comprise one or more inorganic binders and at least one zeolite adsorbent in the form of agglomerated zeolite. The inorganic binder is preferably selected by way of non-limiting example from natural clays, synthetic clays, silica and alumina, etc., preferably natural clays and/or synthetic clays, more preferably natural clays. The presence of the inorganic binder is measured as described herein below.

The content of the inorganic binder in the article is in the range of 0.2 wt% to 30 wt%, preferably in the range of 0.3 wt% to 25 wt%, more preferably in the range of 0.4 wt% to 20 wt% with respect to the total weight of the article. , And even more preferably in the range of 0.5 wt% to 9 wt %.

Zeolite particles present in the articles of the present invention include, for example, beads, pellets, extrudates, crushed beads, crushed pellets, flakes, cracks, and rounded or unrounded, hollow or solid, generally It may have a variety of forms and shapes, such as all kinds of shapes, for example cenospheres as disclosed in US 5856264 and/or mixtures thereof.

According to a preferred embodiment, the at least one zeolite particle in the article has a dimension of 0.1 mm or greater.

Thus, the expression "zeolite particles" means that the weight content of the zeolite powder is less than 90 wt%, preferably less than 70 wt%, more preferably less than 50 wt%, even more preferably less than 25 wt%, based on the total mass of the zeolite particles, It should be understood to include a zeolite adsorbent (agglomerate) and a zeolite powder that is even more preferably less than 10 wt%, and even more preferably less than 5 wt%. The weight ratio of zeolite powder to total mass of zeolite particles is measured by sieving the zeolite particles after dissolution of the resin in a suitable solvent. The amount of zeolite powder by weight is the amount of zeolite particles that pass through a 500 mesh sieve (31 μm).

The zeolite particles in the article of the invention are advantageously of type A zeolite (framework LTA), chabazite (framework CHA), clinoptilolite (framework HEU), EMT (framework EMT), ZSM-5. (Frame type MFI), silicalite-1 (frame type MFI) and faujasite (frame type FAU), more preferably at least one zeolite or a mixture of zeolites selected from FAU type zeolites. Including.

Among the FAU type zeolites, zeolite X, zeolite MSX, zeolite LSX and zeolite Y and mixtures of two or more of these in all proportions are preferred. Zeolite X means a FAU type zeolite having a Si/Al molar ratio between 1.15 and 1.50. Zeolite MSX (Medium Silica X) means a FAU type zeolite having a Si/Al molar ratio between 1.05 and 1.15. Zeolite LSX (Low Silica X) means a FAU type zeolite having a Si/Al molar ratio equal to about 1.00±0.05. Zeolite Y means a FAU type zeolite having a Si/Al molar ratio higher than 1.50.

Among the MFI-type zeolites, the zeolite ZSM-5 means MFI-type zeolite having a Si/Al molar ratio higher than 10, and the zeolite silicalite-1 means aluminum-free MFI-type zeolite.

All of the above-listed zeolites are described, for example, in Atlas of Zeolite Frameworks, Fifth Edition Revised, in the Atlas of Zeolite Framework, published by ELSEVIER on behalf of the Structure Commission of the International Zeolite Association.

The inorganic binder contained in the zeolite particles is preferably kaolin, kaolinite, nacrite, dickite, halloysite, attapulgite, sepiolite, delaminated clay (for example, in gel state), montmorillonite, bentonite, illite and/or metakaolin. And mixtures of two or more of these in any proportion.

Examples of commercially available delaminated clays are for illustrative purposes only Min-U-Gel(R), Pansil(R), Pagel(R), Cimsil(R), Attagel(R), Actigel(R). Etc. Such gels are described, for example, in EP170299 or US6743745.

Thus, the article of the present invention comprises zeolite particles immobilized with at least one resin. Examples of resins suitable for immobilizing the zeolite particles in the articles of the present invention include polymers, especially thermoplastic homopolymers and/or copolymers and polycondensates. Non-limiting examples of polymers include polyolefins, especially low and/or high density and/or ultra high density polyethylene, polypropylene, ethylene copolymers, copolymers of ethylene and vinyl acetate, polyacrylic acid, acrylonitrile homopolymers and/or Or copolymers, polyacrylates, polymethacrylates, acrylate copolymers and/or methacrylate copolymers, polystyrenes and/or styrene copolymers, polyesters, ie homopolyesters and copolyesters, such as polyethylene terephthalate, polybutylene terephthalate, halogenated polymers and halogenated copolymers , For example poly(vinylidene difluoride) polymers (PVDF), poly(tetrafluoroethylene) polymers (PTFE) and/or copolymers of PVDF and PTFE, other fluorinated homopolymers and fluorinated copolymers, polyamides, ie homopolyamides and Copolyamides, for example polyamide 11 and polyamide 12 as described in WO 2014/182861 and WO 2014/055473 and other polyamides with even and odd numbers, aromatic polyamides, polyvinyl chloride, polyurethanes, polyether sulfones, Examples thereof include polyether ketone, polycarbonate, epoxy resin, phenol resin, thermosetting resin and elastomer resin, and mixtures thereof.

Among the polyamide copolymers, mention may be made in particular of polyether block polyamides such as Pebax® sold by Arkema.

According to the first preferred embodiment, examples of resins suitable for immobilizing the zeolite particles in the article of the invention include ethylene copolymers, copolymers of ethylene and vinyl acetate, polyacrylic acid, acrylonitrile homopolymers. And/or copolymers, polyacrylates, polymethacrylates, acrylate copolymers and/or methacrylate copolymers, polystyrenes and/or styrene copolymers, polyesters, ie homopolyesters and copolyesters, such as polyethylene terephthalate, polybutylene terephthalate, halogenated polymers and halogens -Functionalized copolymers, such as poly(vinylidene difluoride) polymers (PVDF), poly(tetrafluoroethylene) polymers (PTFE) and/or copolymers, other fluorinated homopolymers and fluorinated copolymers, polyamides, ie homopolyamides and copolyamides , For example, polyamide 11 and polyamide 12 as described above and other polyamides with even and odd numbers, aromatic polyamides, polyvinyl chlorides, polyurethanes, polyether sulfones, polyether ketones, and the like, A mixture may be mentioned.

According to a second preferred embodiment, examples of suitable resins for immobilizing the zeolite particles in the article of the invention include copolymers of ethylene and vinyl acetate, polyesters, ie homopolyesters and copolyesters, For example, polyethylene terephthalate, polybutylene terephthalate, halogenated polymers and copolymers, such as poly(vinylidene difluoride) polymers (PVDF), poly(tetrafluoroethylene) polymers (PTFE) and/or copolymers, other fluorinated homopolymers. And fluorinated copolymers, polyamides, ie homopolyamides and copolyamides, such as polyamide 11 and polyamide 12 as described above and other polyamides with even and odd numbers, aromatic polyamides and polyurethanes, etc. As well as mixtures thereof.

According to a third preferred embodiment, examples of resins suitable for immobilizing zeolite particles in the articles of the invention include copolymers of ethylene and vinyl acetate, halogenated polymers and halogenated copolymers such as poly. (Vinylidene difluoride) polymers (PVDF), poly(tetrafluoroethylene) polymers (PTFE) and/or copolymers, other fluorinated homopolymers and fluorinated copolymers, polyamides, ie homopolyamides and copolyamides, such as those mentioned above. Mention may be made of polyamide 11 and polyamide 12 as described, as well as other polyamides with even and odd numbers and aromatic polyamides and the like, and mixtures thereof.

Halogenated polymers are preferred, fluorinated polymers are more preferred, and PVDF is even more preferred because it is compatible with the zeolite particles to form the articles of the invention.

Preferred resins are particles having a preferred volume average particle size of less than 100 μm, preferably less than 50 μm, preferably less than 20 μm, more preferably less than 12 μm, more preferably less than 10 μm, preferably beads, agglomerates of beads and aggregates of beads. It is a resin of the form.

As mentioned above, the resin may be selected from polymers, in which case preferred polymers are generally in the range 1 nm to 100 μm, preferably 1 nm to 50 μm, more preferably 1 nm to 20 μm. Is a polymer obtained by an emulsion polymerization process which results in small discrete particle sizes in the range up to. The volume average particle size of the resin is measured using a Microtrac S3500 analyzer. The particles are blended with deionized water and 1% Triton-X100 surfactant, sonicated and then tested.

In the article of the present invention, the particle size ratio [(resin particle size) to (zeolite particle size)] is in the range of 1:20000 to 3:1, preferably 1:10000 to 2.5:1, More preferably, it is in the range of 1:1000 to 2:1.

Examples of resins are organic adhesives or adhesive compositions or binders, such as glues, contact adhesives, containing one or more of the thermoplastic homopolymers and/or copolymers and polycondensates listed above. , A pressure sensitive adhesive.

As previously disclosed herein, the articles of the present invention have a high content in the active material (ie, adsorbent material) expressed as a zeolite content that is greater than or equal to 60 wt% based on the total weight of the article. Content, preferably the zeolite content is more than 70 wt%, more preferably strictly more than 80 wt%, even more preferably exactly more than 85 wt%, even more preferably exactly 88 wt% with respect to the total weight of the article. Ultra, generally 90 wt% or more.

The quantitative amount of zeolite in the article is measured by X-ray diffraction, as described herein below. This high adsorbent material content is 50% to 99%, more preferably 60% to 99%, even more preferably 70% to 99% relative to the free adsorbent material, ie the resinless adsorbent material. Permitting articles having volume efficiencies equal to up to %, and even more preferably up to 80% to 99%.

Volumetric efficiency is measured according to the analytical methods described herein below.

The resin content in the articles of the present invention is measured by thermogravimetric analysis in combination with infrared spectroscopy (TGA-IR). The analysis is performed, for example, by a METLER Toledo TGA-DSC2 instrument in combination with an infrared spectrometer NICOLET™ IR6700. The sample is heated in air from ambient temperature (25° C.) to 1100° C. with a fixed temperature gradient (typically 5° C. per minute). The resin content can be calculated by recording the weight loss as a function of temperature and analyzing the resulting exhaust gas by infrared.

According to another aspect of the invention, the adsorbent article of the invention may further comprise one or more additives. Non-limiting examples of such additives include rheology modifiers, pore formers, processing aids, dispersants, lubricants, tackifiers, UV stabilizers, pigments, dyes, antioxidants, impact modifiers. It can be selected from agents, phase change materials (PCM), flame retardants, flavoring agents and the like. According to one aspect of the invention, the adsorbent article may further include one or more compounds (colored indicators) that are capable of changing color depending on the degree of adsorption of the zeolite. Such compounds are, for example, pigments, inks or dyes which react chemically while changing colors (for examples of reactive inks, see WO 2006/079713).

The adsorbent article can be formed by conventional processing methods such as injection molding, compression molding and extrusion as non-limiting examples. Generally, the method of preparing the articles of the present invention comprises:
a) blending the zeolite particles with at least one resin to form a uniform mixture;
b) adding the homogeneous mixture to a processing device;
c) molding into a desired shape and size,
d) applying sufficient heat to soften the resin,
e) applying pressure to pack the particles to a desired density,
f) a step of binding the resin and the zeolite particles while keeping the temperature and the pressure constant,
g) cooling the resin until it hardens.

The compounding can be accomplished by friction shear compounding using bare hands or mechanical means such as a ribbon blender to spread the compound into a uniform matrix. "Processing device" means any molding device known to those skilled in the art, and may be selected from, for example, extrusion devices, compression molding devices and injection molding devices, as non-limiting examples.

The design of compression molding dies or dies for continuous extrusion requires a relief carved into the tool to allow easy removal and transfer from the molding tool. The design of such molding equipment and tools is well known to those skilled in the art.

Blends of zeolite particles and at least one resin obtained in step a) are likewise part of the invention.

Preferred resins present in the formulation of the zeolite particles according to the invention used during the formulation in step a) above are less than 100 μm, preferably less than 50 μm, preferably less than 20 μm, more preferably less than 12 μm, more preferably Resins in the form of particles, preferably beads, agglomerates of beads and aggregates of beads, having a preferred volume average particle size of less than 10 μm.

The resin present in the formulation of the zeolite particles according to the invention used during formulation in step a) above is advantageously chosen from polymers, the preferred polymers being obtained by polymerization by emulsion polymerization processes. It is a polymer and is generally in the form of having small discrete particle sizes in the range 1 nm to 100 μm, preferably in the range 1 nm to 50 μm, more preferably in the range 1 nm to 20 μm.

In the formulation according to the invention obtained in step a) of the above method, the particle size ratio [(resin particle size) to (zeolite particle size)] is in the range from 1:20,000 to 3:1, preferably 1: It is preferably in the range of 10000 to 2.5:1, more preferably in the range of 1:1000 to 2:1.

Steps b), c), d) and e) may be carried out in an order such that one or more of these steps are carried out simultaneously, or all of these steps are carried out in one or more. It should be noted that the steps may be performed in the order in which they are performed simultaneously. A preferred implementation comprises the steps b), c), d) and e) in succession. Step f) comprises maintaining a constant temperature and pressure for a period of time generally comprised between 1 second and 5 hours, preferably between 1 second and 1 hour. Step f) may be optional in the method of the invention.

The temperature of the molding die in the extruder or compression molding equipment must be high enough to soften the resin and allow the resin to adhere to the zeolite particles, typically the melting point or softening temperature of the resin. About 5 to 10°C higher. As a non-limiting example, for semi-crystalline polymers, the melting temperature is generally at least 5°C above the melting point of the polymer crystallites. For amorphous polymers, the melting temperature is generally 5°C above the softening temperature of the resin.

Pressure is applied during step e). Typical pressures can range from 15 psi (0.1 MPa) to 2500 psi (17 MPa), generally 435 psi (3 MPa) to 2500 psi (17 MPa), depending on the final properties desired.

Once the article reaches the proper hardness, it can be removed from the mold or extruded from the die. The appropriate hardness depends on the resin chosen, but for semi-crystalline polymers the appropriate hardness is more than 5°C below the primary recrystallization temperature at which the crystalline phase can be measured. In the case of amorphous polymers, the hardness temperature is 5°C or more lower than the hardness temperature at which the polymer glass transition point occurs.

Articles are selected from, for example, cubes, parallelepipeds, spheres, sheets, pleated sheets, films, pleated films, cylinders, convex polyhedrons, prisms, cones, ellipses, pyramids, corrugations and helices. Can have any shape.

When in the various shapes listed above, the articles of the invention include various shape elements used to increase surface area, such as protrusions (cones, cylinders, concentric circles, fins and supports). Fins, etc.), holes (tapered and non-tapered holes, non-through holes and through holes, which may include cross-sectional shapes such as circles, polygons, stars, etc.), see, for example, WO2014/055546. I want to. The article may include various channels that may be essentially circular, polyhedral or sinusoidal.

The various shapes defined above may provide improved control of pressure drop within the articles of the invention, which may result in reduced energy consumption during purification or separation processes using the articles of the invention. ..

Thus, the articles of the present invention allow for complete immobilization of sorbent particles, thus avoiding abrasion of the particles together and prolonging the useful life of the article.

According to a further embodiment, the article has a mechanical resistance expressed as compressive strength ranging from 290 psi (2 MPa) to 14500 psi (100 MPa). According to yet a further embodiment, the crush strength of the article of the present invention is generally between 0.05 MPa and 50 MPa, preferably between 0.05 MPa and 30 MPa, more preferably between 0.05 MPa and 20 MPa. Is. Compressive strength and crush strength are measured according to the techniques described herein below.

The articles of the present invention provide the good to very good adsorption and desorption rates required in the applications for which the articles are needed.

In a further aspect, the invention is a method for separating a fluid from one or more other fluids and/or separating a fluid from impurities contained in said fluid, said fluid comprising Dealing with at least one article as hereinbefore described.

The invention further relates to the use of the adsorbent article as hereinbefore described for the drying, conditioning, purification and separation of gases, liquids and vapors. The adsorbent article used in such an embodiment can be regenerated by pressure swing adsorption, heat treatment or solvent washing and subsequent drying.

Articles according to the invention can be used to dry compressed air for applications such as air braking systems. Furthermore, the articles according to the invention can be used for the drying of refrigerants. Articles according to the invention can be used for the drying and desulfurization of liquid hydrocarbons, for the drying and sweetening of natural gas, or for the drying of chemicals such as alcohol, or for the drying of petrochemicals such as crack gas. Can also be used for

A further application of the articles according to the invention may also include air separation in an air separation device in which nitrogen is adsorbed and the air becomes oxygen rich, for example in a unit for breathing air. Furthermore, the articles according to the invention can also be used in air conditioners for drying refrigerating fluids.

The articles according to the invention can be used both for air purification before cryogenic distillation and for CO ₂ removal from air or various natural or synthetic gases.

Finally, the shaped bodies according to the invention can be employed as ion exchangers in water softeners in which the desired effect is achieved by the exchange of calcium and sodium.

FIG. 1 is a cross-sectional view of an example of the article (A) according to the present invention. The article comprises zeolite particles (1) together with at least one zeolite adsorbent, said particles being immobilized by at least one resin (2).

FIG. 1bis is a SEM image of a cross section of the article according to the invention illustrated by FIG. Articles are prepared with 95 wt% Siliporite® Nitroxy® SXSDM agglomerates (beads in FIG. 1) and 5 wt% Dakota UNEX EVA T1 (0 μm to 200 μm grade) resin. The beads are adhered to each other by a resin bridge at the contact point. One of the advantages of resin crosslinking is that the majority of the bead surface remains resin-free, which allows for volumetric efficiency optimization.

The article (A) of FIG. 1 is shown in FIG. 2, which is a cross-sectional view of an example of the adsorbent cartridge (B). The cartridge (B) is an assembly of the article (A) inserted in a container (6) (made of polymer or metal such as aluminum), with no channels in the wall of the container to force fluid into the article. A cap provided with a seal housing (7) between the article and the wall of the container and secured by screws (4) and seals (5) (O-rings are shown) to prevent formation. (3, 3'). The flow at the inlet (10) is distributed through the flow distribution section (8) and the filter (9). A purified or separated stream is produced at the outlet (11).

FIG. 3 is a sectional view of another example of the cartridge (C) using the article (A). The article is directly attached to the container (14) by the resin (2), and no channel is formed to force fluid into the article. The caps (13, 13') are sealed to the receiving container (14) and the flow distribution area (12). The flow at the inlet (10) is distributed through the flow distribution area (12). A purified or separated stream is produced at the outlet (11).

FIG. 4 is a cross-sectional view of an example of a cartridge (D) using the article (A). The cartridge (D) is an assembly of an article (A) loaded in a container (15) (made of polymer or metal such as aluminum) and a cap (14) fastened by screws (4). .. The flow at the inlet (10) is distributed from axial to radial. A purified or separated stream is produced at the outlet (11) and becomes radial to axial.

FIG. 5 is a SEM image of the dried formulation obtained in step a) of the method described herein above, ie, before being immobilized by compression molding. The formulation consisted of 88 wt% Silporite® Nitroxy® SXSDM beads from CECA and 12 wt% Arkema Kyblock™ FG-81 resin. SEM images were created by coating a thin layer of iridium using an ion beam coater from Southbay Technologies, model IBSe. SEM images were obtained by field emission SEM with Hitachi SU8010. This image shows the compatibility of a fully dispersed coating of Kyblock™ FG-81 resin on the surface of Siliporite® Nitroxy® SXSDM beads.

FIG. 6 is an SEM image of another example of a dried formulation without inorganic resin obtained in step a) of the method described hereinabove, ie, before being immobilized by compression molding. Is. The formulation consisted of 88 wt% Silporite® NK30 zeolite powder from CECA and 12 wt% Arkema Kyblock™ FG-81 resin. SEM images were created by coating a thin layer of iridium using an ion beam coater from Southbay Technologies, model IBSe. SEM images were obtained by field emission SEM with Hitachi SU8010. This image shows the compatibility of a fully dispersed coating of Kyblock™ FG-81 resin on the surface of Siliporite® NK30 zeolite powder.

The invention is further described by the following examples, which are not intended to impose any limitation on the scope of protection sought to be obtained, as set forth in the appended claims.

Example 1 is a compression molded cylindrical shape according to the invention consisting of 80 wt% CECA Siliporite® Nitroxy® SXSDM beads (lithium exchanged LSX zeolite) and 20 wt% Arkema Kyblock™ FG-81 resin. Is an adsorbent article. The article of Example 1 has a high bulk density and very good mechanical integrity. To make this article, 20 wt% Arkema Kyblock™ FG-81 resin is added to 80 wt% CECA Siliporite® Nitroxy® SXSDM beads with an average particle size of 0.52 mm. Kyblock™ FG-81 is sold as a volume average size agglomerate from 1 μm to 10 μm, which agglomerates consist of resin particles with an average volume size from 150 nm to 300 nm.

Manually mix the two components for 15 minutes in a mixing bowl with a synthetic mixing paddle using a low shear swiping technique until the binary blend is a homogeneous mixture. Make a homogeneous mixture. While mixing, preform the forming die in the oven at 180°C. As soon as the forming die has reached an equilibrium temperature of 180° C., the mixture is added into a forming die with a diameter of 5.42 cm and compressed with a pressure of 87 psi (0.6 MPa) for 1 minute. The article is then manually removed and placed in an oven preheated to 180° C. for 5 minutes to fully cure the article. The article is then removed and allowed to cool to room temperature in a closed container to prevent moisture adsorption by the article.

The final article has dimensions of 5.42 cm diameter and 3.95 cm height. The LSX zeolite content analyzed by XRD is 66 wt% based on the total weight of the article. The following characteristics of the article have been measured according to the techniques described herein below.
Crush strength value: 0.5 MPa.
Worn value: 0.6%.
Volumetric efficiency: 0.130 g cm ³ .

Example 2 is a compression molded cylindrical adsorbent article consisting of 95 wt% CECA Siliporite® Nitroxy® SXSDM beads and 5 wt% Arkema Kyblock™ FG-81 resin. The article of Example 2 has a high bulk density and very good mechanical integrity. To make this part, 5 wt% of Arkema Kyblock™ FG-81 resin is added to 95 wt% of CECA's Siliporite(R) Nitroxy(R) SXSDM beads. The LSX zeolite content analyzed by XRD is 79 wt% based on the total weight of the article.

The two components are manually mixed in a mixing bowl with a synthetic mixing paddle for 15 minutes using a low shear swipe method until the binary blend is uniform to a uniform mixture. While mixing, preheat the forming die in the oven to 180°C. As soon as the forming die has reached an equilibrium temperature of 180° C., the mixture is added into a forming die with a diameter of 5.42 cm and compressed with a pressure of 87 psi (0.6 MPa) for 1 minute. The article is then manually removed and placed in an oven preheated to 180° C. for 5 minutes to fully cure the article. The article is then removed and allowed to cool to room temperature in a closed container to prevent moisture adsorption by the article. The final article has the dimensions of 5.42 cm diameter and 3.59 cm height. The following characteristics of the article have been measured according to the techniques described herein below.
Crush strength value: 0.3 MPa.
Worn value: 0.8%.
Volume efficiency: 0.168 g cm ³ .

Example 3 is prepared according to Example 1 using 95 wt% CECA Siliporite® Nitroxy® SXSDM beads and 5 wt% Dakota UNEX EVA T1 resin (grade from 0 μm to 200 μm). The LSX zeolite content analyzed by XRD is 79 wt% based on the total weight of the article. The following characteristics of the article have been measured according to the techniques described herein below.
Crush strength value: 2.6 MPa.
Worn value: 1.3%.
Volume efficiency: 0.164 g cm ³ .

Example 4 is prepared according to Example 1 using 95 wt% CECA Siliporite® Nitroxy® SXSDM beads and 5 wt% Dakota UNEX EVA T1 resin (grade from 0 μm to 80 μm). The LSX zeolite content analyzed by XRD is 79 wt% based on the total weight of the article. The following characteristics of the article have been measured according to the techniques described herein below.
Crush strength value: 1.3 MPa.
Worn value: 0.7%.
Volumetric efficiency: 0.172 g cm ³ .

Example 5 was prepared using 95 wt% CECA Siliporite(R) Nitroxy(R) SXSDM beads and 5 wt% Arkema Orgasol(R) 2002 D NAT1 resin to give a particle size of 20±2 μm. Is prepared according to. The LSX zeolite content analyzed by XRD is 79 wt% based on the total weight of the article. The following characteristics of the article have been measured according to the techniques described herein below.
Crush strength value: 2.0 MPa.
Worn value: 0.5%.
Volumetric efficiency: 0.163 g cm ³ .

Example 6 was prepared using 95 wt% CECA Siliporite® Nitroxy® SXSDM beads and 5 wt% Arkema Orgasol® 2002 ES6 NAT3 resin to give a particle size of 60±3 μm. Is prepared according to. The LSX zeolite content analyzed by XRD is 79 wt% based on the total weight of the article. The following characteristics of the article have been measured according to the techniques described herein below.
Crush strength value: 2.2 MPa.
Worn value: 0.7%.
Volumetric efficiency: 0.160 g cm ³ .

Example 7 is the use of an article of the invention in a stationary medical oxygen concentrator sold under the name EverFlo™ by Philips Respironics. Such medical oxygen concentrators use pressure swing adsorption (PSA) methods to produce oxygen by extraction of nitrogen from an ambient gas mixture, which is typically air. The EverFlo™ concentrator uses two cylindrical cartridges packed with free zeolite particles.

In a comparative experiment, the free zeolite particles present in the cylindrical cartridge have been replaced by two articles according to the invention in which the zeolite particles are bound by a resin. In this comparative test, two articles are cast directly into two cartridges of an EverFlo™ concentrator (fill the same volume and compress with a pressure of 0.6 MPa). The article consisted of 95 wt% CECA Siliporite® Nitroxy® SXSDM beads and 5 wt% Arkema Kyblock™ FG-81, similar to the preparation in Example 2.

The concentrator is operated for 6 months (continuous operation with the production flow rate set to a fixed value of 3 L min ⁻¹ ). During 6 months of continuous operation, the O ₂ purity measured at this production flow rate was similar in both experiments, which indicated the presence of resin binding the zeolite particles. It has been shown that it does not affect the purity of oxygen produced.

After a period of 6 months, the cartridge containing the article of the invention is opened and the presence of fines (dust) is visually assessed. It is observed that no dust is present in the cartridge and no free beads are present in the cartridge.

Characterization method
Zeolite Particle Structure and Average Particle Size Zeolite particle morphology and shape (structure) are observed by scanning electron microscopy (SEM). The average particle size of the zeolite particles present in the article is the number average of the largest dimensions of the zeolite particles observed by SEM.

Several photographs of polished cross sections prepared by ion polishing have been taken at a magnification of at least 50 times. The maximum size of at least 200 zeolite particles is measured by dedicated software, such as ImageJ (http://www.imagej.net). The accuracy is about ±3%.

Presence of Inorganic Binder in Zeolite Particles The adsorbent article is immersed in a solvent selected to dissolve the resin or heated in air to decompose the resin by combustion. The nature and concentration of zeolite in the resulting particles is measured by XRD. The inorganic binder corresponds to the rest of the article after removing the resin and subtracting out the crystalline portion (zeolite portion).

Further, the polished cross section of the obtained particles is prepared by ion polishing. Scanning electron microscopy analysis combined with energy dispersive X-ray spectroscopy was performed on the polished cross-sections to analyze the different tissue types and the chemistry of each type of element within the associated particles (zeolite, binder). To confirm the composition. The inorganic binder is the part of the particle that is not zeolitic.

Zeolite Content Zeolite content, ie, the total weight content of zeolite moieties in an article, is determined by X-ray diffraction analysis known to those skilled in the art under the acronym XRD. This quantitative and qualitative analysis was carried out by comparing the diffraction pattern of the article with the data in the ICDD databank using a Bruker instrument, the amount of zeolite or the amount of each zeolite type being determined by Brucker's TOPAS software. To be evaluated. The zeolite weight content is equal to the sum of the contents of all zeolites.

Volumetric efficiency Volumetric efficiency corresponds to the amount of adsorbed water in a cylindrical article sample with a diameter of 5 cm and a height of 3 cm. The sample is placed for 24 hours at 23° C.±2° C. in a closed container with a relative humidity of 50%, as described in patent application EP 1223147A.

Water adsorption values are measured by weighing the sample before and after this 24 hour period. Volumetric efficiency is the weight gain of the sample divided by the volume of the cylinder (58.9 cm ³ ).

The sample may be a material according to the invention (article in which zeolite particles are bound by a resin), or without resin, packed under pressure of 1 MPa and filling a cylinder of the same diameter and height. It may be a sample of zeolite particles.

The volumetric efficiency ratio is the ratio of the volumetric efficiency of the article of the invention to the volumetric efficiency of the above sample of resinless zeolite particles.

The volume average particle diameter The volume average particle diameter of the resin (polymer) particles, using 100mL glass beaker is measured by directly adding the resin particles of 0.5g of 10% Triton X-100 aqueous solution of 2 mL. The resin powder and surfactant are mixed well and then the mixture is diluted by adding 60 mL of deionized water to the beaker. A beaker is placed in the ultrasonic generator to disintegrate the agglomerates while continuing to stir the solution to prevent settling of the powder. The solution is used to measure particle size distribution in a Microtrac S3500 analyzer.

Mechanical properties: compressive strength, crush strength and abrasion resistance
Compressive Strength : A Zwick tensile/pressure tester, model UP1455 is utilized to measure the compressive strength of articles of the present invention. For the measurement of this compressive strength, a cylindrical article having a specimen diameter of 5 mm is cut to a specimen length of 7 mm. To reproducibly and precisely measure the compressive strength, it must be ensured that the front faces of the articles are planar and parallel. The measurement is performed at room temperature. The force applied in advance is 1N. The experiment is carried out at a test speed of 1 mm/min. The test force acts on the front side.

Crush Strength : Another Instron tensile/pressure tester, model 4505, cell 10 kN S/N UK1280, also had a sample diameter of 60 mm and a sample length of It is used for a 10 mm cylindrical article. For rigorous and reproducible crush strength measurements, it must be ensured that the front faces of the articles are planar and parallel. The measurement is performed at room temperature. The experiment is performed at room temperature (23° C.) at a test speed of 1 mm/min. The test force acts on the front through a 150 mm plate.

Abrasion resistance : Wet abrasion test is performed under the following conditions. A 136 mL cylindrical article having a test material diameter of 5 mm and a test material length of 7.5 mm is placed in a cylindrical 150 mL container having a diameter of 4.4 cm and a height of 10 cm. Add 68 mL of ethanol, close the vessel and vortex for 30 minutes in a Model 30 Red Devil Paint Conditioner at high frequency. The fines produced by attrition are measured. After this, the granules are rinsed from the article sample with ethanol as they enter the beaker through a 1.25 mm standard sieve, isolated from ethanol, heated to 80° C., dried and weighed. The weight obtained is expressed as a weight percent relative to the initial charge.

Claims (15)

An adsorbent article comprising zeolite particles of at least one zeolite adsorbent, said particles being immobilized by at least one resin, wherein the average particle size of said at least one zeolite adsorbent is: 0.03 mm to 3 mm, the zeolite content is 60 wt% or more based on the total weight of the article,
The zeolite particles are A-type zeolite (framework LTA), chabazite (framework CHA), clinoptilolite (framework HEU), EMT (framework EMT), ZSM-5 (framework MFI), silicalite- 1 (framework MFI) and faujasite (framework FAU) at least one zeolite or mixture of zeolites selected from the group consisting of:
Said zeolite particles in said article comprising at least one inorganic binder selected from natural clay, synthetic clay, silica and alumina and at least one zeolite adsorbent in the form of agglomerated zeolite;
Said at least one resin comprises copolymers of ethylene and vinyl acetate, homopolyesters and copolyesters, halogenated polymers and copolymers, homopolyamides and copolyamides, and/or mixtures thereof,
Adsorbent articles. The zeolite particles are beads, pellets, extrudates, crushed beads, crushed pellets, flakes, cracks, and rounded or non-rounded hollow or non-hollow shapes selected from almost all types, and Article according to claim 1, having the form and/or shape of/or a mixture thereof. The article of claim 2, wherein the morphology and/or shape is a cenosphere. Article according to any one of claims 1 to 3, wherein at least one zeolite particle in the article has a dimension of 0.1 mm or greater. 5. The zeolite according to claim 1, wherein the FAU-type zeolite is selected from among zeolite X, zeolite MSX, zeolite LSX and zeolite Y and mixtures of two or more of these in all proportions. Goods. The zeolite particles are inorganic selected from kaolin, kaolinite, nacrite, dickite, halloysite, attapulgite, sepiolite, delaminated clay, montmorillonite, bentonite, illite and metakaolin and mixtures of two or more thereof in any proportion. An article according to any of claims 1 to 5, containing a binder. 7. An article according to any of claims 1 to 6 , wherein the content of active material (i.e. adsorbent material) in the article is 60 wt% or more, expressed as weight zeolite content relative to the total weight of the article. The shape is selected from among cubes, parallelepipeds, spheres, sheets, pleated sheets, films, pleated films, cylinders, convex polyhedrons, prisms, cones, ellipses, pyramids, corrugations and helices. The article according to any one of 1 to 7 . An article according to any one of which is used to increase the surface area, including the shape element selected from protrusions and holes, claims 1-8. The protrusions are selected from the group consisting of cones, cylinders, concentric circles, fins and fins with supports, and/or the holes are tapered and non-tapered holes, non-through holes and through holes, circles, polygons The article of claim 9 , which may also include a star and/or star cross-sectional shape. An article according to any of claims 1 to 10 , comprising channels which are circular, polyhedral or sinusoidal. An article according to any of claims 1 to 11 , having a mechanical resistance expressed as compressive strength in the range of 290 psi (2 MPa) to 14500 psi (100 MPa). To isolate the fluid from one or more other fluids, and / or some fluid to a method for separating from impurities contained in the fluid, any one of claims 1 to 12 to said fluid A method comprising contacting with at least one article according to. 14. The method of claim 13 for drying, conditioning, purifying and separating gases, liquids and vapors. A blend of at least one zeolite particles and at least one resin,
The average particle size of the at least one zeolite particle is in the range of 0.03 mm to 3 mm, the zeolite content is 60 wt% or more based on the total weight of the formulation,
The zeolite particles are A-type zeolite (framework LTA), chabazite (framework CHA), clinoptilolite (framework HEU), EMT (framework EMT), ZSM-5 (framework MFI), silicalite- 1 (framework MFI) and faujasite (framework FAU) at least one zeolite or a mixture of zeolites,
Said zeolite particles comprising at least one inorganic binder selected from natural clay, synthetic clay, silica and alumina and at least one zeolite adsorbent in the form of agglomerated zeolite;
Said at least one resin comprises copolymers of ethylene and vinyl acetate, homopolyesters and copolyesters, halogenated polymers and copolymers, homopolyamides and copolyamides, and/or mixtures thereof,
The formulation, wherein the at least one resin is in the form of particles and the particle size ratio [(resin particle size) to (zeolite particle size)] is in the range of 1:20000 to 3:1.

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